Method of vulcanizing caoutchouc and the product derived therefrom



PA T CE oam B; SEBBELL, or AKRON, OHIO, vAssaenon To THE GOODYEAR TIRE & RUBBER- Patented Oct. 21,1930

, comimnm orhxnOn, 0310,45 conrona'r'ron or OHIO METHOD or v LoAnIzrnG CAOUTCHOUC AND THE rRoDUcr DERIVED 'II IEREFROM No viewing. Application filed September13, 1927. Serial No. 219,365;

invention relates to the treatment of riod. Also, water and hydrogen sulphide "r'ubberand it has for its primary object the are given ofi as is evident from the odor --provision of a desirable material for'accelerand the appearance of the condensate. The

atingthevulcanizationof rubber products. product obtained is a thick semi-solid which condensation product; 1

"properties."'The generalformula of a Schifi?" p 7 I: n

- The accelerative properties of the *material I prepared according to the method discussed weretested in the above formula and the results "obtained are tabulated in the follow- More specifically my invention has for one iot its objects the provision of an accelerator which is composed of the reaction products of armercaptothiazole and an aldehyde amine It has previousl y beenlmown that mercaptothiazoles were powerful accelerators ofth'e T vulcanization-ofrubber products. It has also "been known that the mercaptothia'zoles might be caused to react with other substances, such as metallic salts, aldehydes, ammonia and amines, to produce accelerators which were, in many cases, superior to the'mercaptothiazoles from which they were derived. which insures excellent results I have-made the discovery that'mercapto- Q V x I r Parts thiazoles, such as mercaptobenzothiazoles, F Q 'QP rubber '-v--'-' "19 may be caused toreact with-aldehyde amine Z1110 sl 5 condensation products,known as Schifl bases, f l e -r l to produce'accelerators having very desirable m 'j-f' ---Y- .-'---L- Accelerator 0,50

base is representedasjfollows: ,7

The, radicalsjindicated by thecharacters R Thisclass of compounds includes the reao- I 7 tion products of. crotonaldehyde and aniline,

ihcnmic.reecti ni alses place duri liis. P

tilling off a little aniline. The chemical formula of the reaction product} is unknown.

It is to beunderstood that this method of preparing the reaction product of the mercaptothiazole and the Schiff bases is of'gen 'eral application, and may be employed to manufacture various other materials of this class, which have been mentioned.

The material prepared-according to the above: described method-may be incorporated .intovarious rubber compounds; 'rThe following is aisample formula ot a compound a 111g tables.

TABLE I 1 Merccptoten zjothiczfol e control (crotylidene aniline), iacejtaldehydefand ani- CF I o V a q g line (ethylidene aniline), crotonaldehyde i a g lg 523}? methylamine, propyl aldehyde and ethyl- 33: e -la e -l i -l atbreak amine, butyl aldehyde, aniline, butyl aldef. hyde toluidine,heptaldehyde aniline heptal- 7 20 13 v m 940 dehyde butylamine, anlline c nnamic ald e. fig egg Q iv hyde, and numerous other hydrocarbon com- 90 20 V 28 V 102 I 180 pounds which include the grouping indicated Y in the formula. w i TABLE II] A specific examplerof a compound which 1 Z falls within the scope of my invention is the V l 7 crotonaldehyde aniline; ,mercaptobenzo- V thiazo'le' reaction product. This, material lii 506% I Tnsfle Ferment may be prepared as follows: 7 a Timeifi a 1kclsofigl.1 kelsofigil tr l l i a l o l Intermix molecular quantities of the. merm f 1 g captobenzothiazole and-the crotonaldehyder v anilineireaction products, ,and reflux them 1, 20 20 No cure 885 ftor a period of two hours or more. I An eXo- ,3 68 870 TABLE III C'rotonaldchydeAnllmcMcrcaptobenzothiaaolc Cure 500% 700% Tensile Per cent elong. elong. strength elong. Time in Pounds kgs./crn kgs/cm kgs/cm at break min. pressure TABLE IV Mcrcaptobenzothiazole solid ethyltdene aniline Cure 500% 700% Tensile Per cent elong. elong. strength elong. Time in Pounds kgsv cm kgs./crn kgs./cm at break min. pressure Tables I and II respectively contain data obtained by testing samples in which the pure mercaptobenzothiazole and crotylidene aniline were used as accelerators. Table III contains data obtained from tests conducted upon samples containing the reaction product of merca-ptobenzothiazole and the crotonaldehyde aniline condensation product. Table IV contains data obtained from the testing of rubber samples containing the re action products of mercaptobenzothiazole and ethylidene aniline. Comparison of the data contained in Tables I and II withthat contained-in Tables III and IV clearly indicatesthat the reaction products of the mercaptothiazoles and the Schiif bases are materially more powerful accelerators than either mercaptothiazole o-r crotylidene aniline alone. 7

Since the product resulting from the combination of the thiazole and the Schiii"s base is a more powerful accelerator than either ofthe original compounds, it is evident that a true chemicalreaction takes place. The latter fact may be further demonstrated by extracting the final product With an alkali. The latter treatment would remove any unreacted mercaptobenzothiazole in its original state. Since no free mercaptobenzothiazole is thus obtained, it is clear that it has combined with the Schifis base.

Although I have disclosed only the preferred embodiments of my invention and described those embodiments in detail, it will be apparent to those skilled in the art that the invention is not so limited, but that various minor modifications may be made therein without departing from the spirit of the invention or from the scope of the appended claims.

What I claim is:

1. A method of treating rubber which comprises heating a vulcanizable rubber compound containing a reaction product of mercaptobenzothiazole with a condensation product of a straight chain aldehydeand an amine having the formula RNH in which R is a benzene group.

mercaptobenzothiazole with the condensation product of aliphatic aldehyde and aniline.

4. A method of treating rubber which comprises heating a vulcanizable rubber compound containing a reaction product of mercaptobenzothiazole with the condensation product of crotonaldehyde and aniline.

5. A method of treating rubber which comprises heating a vulcaniza'ble rubber compound containing a reaction product of mercaptobenzothiazole with the condensation product of an aliphatic aldehyde and aniline.

6. A method of treating rubber which comprises heating a vulcanizable rub'ber compound containing a reaction product of mercaptobenzothiazole with the condensation product of an unsaturated aldehyde and abenzene substituted amine.

'7. The method of treating rubber which comprises heating a vulcanizable rubber compound containing a reaction product of mercaptobenzothiazole and crotylidene aniline.

8. A method of treating rubber which comprises vulcanizing it in the presence of a reaction product of mercaptobenzothiazole and crotylidene aniline.

.9. A rubber product which has been vulcanized in thepresence of a reaction product dehyde.

11. A method of accelerating the rate of vulcanization of rubber which comprises subjecting a vulcanizable mixture of rubber to heat in the presence of a reaction product of mercaptobenzothi'azole, an aliphatic aldehyde containing not more than seven carbon atoms, and a basic benzene substituted amine.

12. A method of accelerating the rate of vulcanization of rubber which comprises subjecting it to heat in the presence of a reaction product of 'mercaptobenzothiazole,

croton aldehyde and a benzene substituted amine.

13. A method of accelerating the rate of vulcanization of rubber which comprises 7 heating a vulcanizable mixture of rubber'in the presence of a reaction product of mercaptobenzothiazole, an aliphatic aldehyde containing not more than seven carbon atoms, and a primary. aromatic amine con taining a single benzene nucleus.

14. A method of accelerating the rate of vulcanization of rubber. which comprises heating a vulcanizable mixture of rubber in the presence of a reaction product ofmercaptobenzothiazole, an aliphatic aldehyde containing not more than seven carbon atoms, and an amine containing a single ben-' zene nucleus.

15. 'A method of accelerating the rate of vulcanization of rubber which comprises subjecting the vulcanizable rubber compound to heat in the presence of a reaction product of mercaptobenzothiazole, croton aldehyde and aniline.

16. A mcthod of accelerating therate of vulcanization of rubber which" comprises subjecting the vulcanizable rubber" com pound to heat in the presence of a reaction product of mercaptobenzothiazole, an aliphatic aldehyde containing not more than seven carbon atoms, and an amine selected from a group comprising aniline, toluidine, methyl amine and ethylamine.

17. A method of accelerating the rate of vulcanization of rubber which comprises subjecting a vulcanizable mixture of rubber to heat in the presence of a material formed by interacting mercaptobenzothiazole with a reaction product of an aliphatic aldehyde containing not more than seven carbon atoms and a benzene substituted amine; I

18. A method ofaccelerating the rate of vulcanization of rubber which comprises subjecting a vulcanizable mixture of rubber to heat in the presence of a material formed by interacting mercaptobenzothiazole with a reaction product of an aliphatic aldehyde containing not more thanseven carbon atoms and a primary benzene substituted amine.

In witness whereof, I have hereunto I signed my name.

Signed at Akron, in the county of Summit and State of Ohio, this 12th day of September, 1927.

LORIN B. SEBRELL. 

